Reaction product of a compound capable of reacting with hydroxyl groups, with an etherification product of a polyglycidyl ether



United tates Patent C REACTION PRODUCT OF A COB/ POUND CAPA- BLE OF REACTENG WITH HYDROXYL GROUPS, WITH AN ETFERIFICATION PRODUCT OF A PQLYGLYCEDYL ETHER Gustav Widmer, Basel, and Paul Zuppinger, Binningen,

Switzerland, assignors to Ciba Limited, Basel, Switzerland, a Swiss firm No Drawing. Griginal application December 15, 1952, Serial No. 326,151, now Patent No. 2,700,030, dated January 18, 1955. Divided and this application January 17, 1955, Serial No. 432,396

Claims priority, application Switzerland December 21, 1951 2 Claims. (Cl. 26043) The invention of U. 8. application Ser. No. 326,151, filed December 15, 1952, now Patent No. 2,700,030, provides an etherification product of a poly-glycidyl ether of a poly-hydroxy-compound, which contains at least two hydroxyl groups and is otherwise free from substituents capable of reacting with epoxide groups, with a higher monohyclric alcohol contining a carbon chain of more than carbon atoms. It also includes a process for the manufacture of the aforesaid products, wherein the higher alcohol is reacted with the poly-glycidyl-ether, and advantageously there is used for at least one mol of the higher alcohol a quantity of the polyglycidyl ether corresponding to one epoxide gram equivalent.

The present application is a division of said U. S. application Ser. No. 326,151 and provides a composition of matter comprising the reaction product of (a) the etherification product of a polyglycidyl ether as claimed in U. S. application Ser. No. 326,151 and (b) a compound capable of reacting with hydroxyl groups, selected from the group consisting of condensation products containing methylol groups obtained from formaldehyde and a compound capable of yielding therewith hardenable products, the methylol groups of the condensation products being at least partially etherified with a lower alcohol containing l'4 carbon atoms. It also includes a process for the manufacture of said products.

As polyhydroxy compounds, which contain at least two hydroxyl groups and are free from substituents capable of reacting with epoxide groups, there come into consideration polyhydric aliphatic alcohols such as glycol or glycerine, or polyhydric, more especially dihydric, phenols such as resorcinol and the like. Especially interesting, however, are polyhydric polynuclear phenols, such as 4:4'-dihydroftydiphenyl-dimethyl methane.

As polyhydroxyglycidyl ethers of polyhydroxy compounds there are suitable products such as are obtainable in known manner, for example, by the reaction of aliphatic polyhydroxy compounds with epichlorhydrin in the presence, for example, of sulfuric acid, followed by treatmentof the resulting polychlorhydrin ethers with alkalis. There may also be used products obtained by reacting aromatic polyhydroxy compounds with epichlorhydrin or dichlorhydrin in the presence of an aqueous alkali by a method in itself known. The reaction products obtained by this process are in very few cases unitary compounds, but are almost always mixtures which consist predominantly of polyglycidyl ethers having chains of different lengths carrying terminal epoxide groups, and, if desired, intermediate hydroxyl groups.

As monohydric alcohols containing a carbon chain of more than 10 carbonatoms, which are reacted with the polyglycidyl ethers in accordance with the invention, there come into consideration saturated orrunsaturated, aliphatic or cyclic alcohols or mixtures of such alcohols. There may be mentioned for example: Undecyl alcohol, dodecyl alcohol, cetyl alcohol, octadecyl alcohol, myricyl alcohol, oleyl alcohol, linolenyl alcohol, linoleyl alcohol and abietinol, and also the glycol monoethers or glycerine diethers of such alcohols. Very suitable also are alcohols or mixtures thereof, which are obtainable by the reduction of higher fatty acids obtained, for example, by the oxidation of parafiin wax, and also higher alcohols obtainable by total synthesis from carbon monoxide and hydrogen, or mixtures of such alcohols, and furthermore commercial mixtures of alcohols such as are obtainable, for example, by reduction with sodium and alcohol or by other methods from drying, semi-drying, oven-drying or non-drying triglyceride oils, for example, linseed oil, soya bean oil, dehydrated castor oil, poppy seed oil, hemp seed oil, cotton seed oil, coconut oil, cod liver oil, whale oil, menhaden oil, sperm oil, tall oil or tall oil esters, and the like.

The polyglycidyl ethers used as starting materials and the etherification products obtainable therefrom in accordance with the invention are characterized by determining their content of epoxide groups and groups capable of esterification, and from these values their content of hydroxyl groups is calculated in the manner described below. The values so obtained are expressed as the number of gram equivalents per kilogram of the product to be characterized, and are hereinafter referred to as Ep-Equ/kg, V-Equ/kg. and OH-Equ/kg, respectively. As one Ep-Equ corresponds to two V-Equ the number of OH-Equ/ kg. can be calculated in a simple manner from the number of V-Equ/kg. by subtracting the number of Ep-Equ/kg. multiplied by 2. In order to determine the two last mentioned values there is used the method described in Bulletin der Schweizerischen Vereinigung der Lackund Farbenchemiker und -Technicker, International Session, Basle, llth-12th May 1949, 3rd special number, page 56. In the absence of epoxide groups the V-Equ is identical with the OH-Equ.

From the foregoing it will be understood that one epoxide-gram equivalent (Ep-Equ) of a polyglycidyl ether having x Ep-Equ/kg. corresponds to a quantity of grams of the polyglycidyl ether.

The reaction between the polyglycidyl ether and the higher alcohol can be carried out even at a low temperature, for example, at room temperature, in which case the use of a very active catalyst, such as boron trifluoride is indispensible. As a rule, however, the reaction is carried out at a higher temperature, in which case the use of a catalyst is of advantage although not always essential.

The reaction of the polyglycidyl ether with the higher alcohol may be carried out in the presence of a suitable solvent for example, dioxane, which is especially ad vantageous or may even be indispensible, when the reaction components are only sparingly or not at all miscible with one another to produce a homogeneous mixture.

The reaction components, including a solvent or a catalyst, maybe mixed together in any desired sequence. However, it is advantageous to add the dissolved polyglycidyl ether in portions or continuously to the heated higher alcohol admixed with the catalyst. Alternatively, the polyglycidyl ether may be mixed with the higher alcohol, and the mixture heated, if desired, with the addition of a catalyst, such as boron trifiuoride, sodium hydroxide or sulfuric acid.

It will be understood that 'the temperature at which the reaction mixture must be maintained depends on the t f a 2,824,850

nature of the starting materials: used and on whether a catalyst and/or a solvent is used." In general the temperature is in the vicinity of the boiling point of the solvent if a solvent is used, and when working without asolvent thetemperature should be at least high enough to enable a homoge' eous mixture to be obtained, for example, by stirring. When decomposition phenomena are likely to occur during the reaction, it may also be carried out in the presence of "an inert gas, such as.

' nitrogen.

In general the reaction is continued until epoxide groups are no longer detected in the reaction mass.

After the reaction any catalyst or solvent may 'be eliminated, if its presence is undesired in the further use of the etherification product. Thus, the catalyst may be eliminated, for example, by neutralization and separation of the resulting salt by filtration, and the solvent may be removed by distillation, advantageously under reduced pressure.

The products so obtained are almost always mixtures of etherification products with unreacted higher alcohol, which products can be used for a wide varietyof purposes directly or after distilling off the unchanged higher alcohol, advantageously under reduced pressure.

The expression etherification products'of polyglycidyl ethers is used herein to denote the mixtures still containing unreacted higher alcohol and also the products freed from such alcohol. 7 I Owing to'their stability to the action of alkalis the etherifica'tion products still containing the unchanged higher alcohols or freed therefrom are valuable substances, which are liquid, oily. to salve-like orsolid depending on the" nature of the starting materials used, and which'owing to the presence of HO-groups and, if desired, unsaturated bonds are capable of undergoing 1 further reaction. As substances capable of reacting with HO-groups, which may beused for after-treating the products, there may be mentioned condensation" products containing methylol groups and obtained from formaldehyde and a compound yielding hardenable products with the latter, such as phenol, ,urea or an aminotriazine containing atleast two NH; groups, for example, melamine, benzoguanamine, acetoguanamine or formoguanamine,

' the methylol groups of thejcondensation product 'being at least partially etherified witha lower: alcohol contain ing 1 to 4 carbon atoms. When the polyglycidyl ethers are reacted with unsaturated higher alcohols the resulting products may be polymerized in the usual manner before or after the subsequent treatments described above.

By these after-treatments the resulting etherification products can be further modifiedto suit the purpose for which they are to be used.

The invention also includes the aforesaid after-treatments and the resulting modified and, ,if'desired polymerized etherification products.

' The etherification products of polyglycidyl ethers and especially the modified products obtainable by the .aforee said afterrtreatments, are suitable for a very wide variety 7 of purposes, especially for the'production of lacquers, if desired, in admixture with other lacquerr-forming sub,

stances which are compatible with the etherification products, for example, alkyd resins, epoxide resins, sty'renized oils .orother' oil-containing binding a'gentsand the like, and also formaldehyde condensation products of phenol, urea or aminotriazines, such as melamine. .tion products ofsuch unsaturated alcohols as are obtainable forexample, from semi-drying oils by reduction,

generally yieldafter the addition of one of the usual drier's, such as a manganese,'lead or cobalt vdrierfliery good oven-drying lacquers. Etherification products'derived from highly unsaturated alcohols, for example,

from linseed oil' fatty alcohol, have good oven-drying properties, and after the addition 'of a drier good dryingpropertiesr e r The following examples illustrate the invention, the parts and percentages being by weight, and the pressures being given in millimetres of mercury (mm. Hg)."

Example 1 7 554 partsof linseed oil fatty alcohol (2 mols) having an iodine number (JZ) of about 166 (methods described f by Turpenen in the Journal of the American Chemical Society, volume 60, pages 567 [1938.], ,were mixed with 0.424 part of boron trifluoride dissolved in anisole, and the mixture was heated in a hawk fitted with stirring means to about 70 C. '424 p'arts '(2'Ep Equ) of the polyglycidyl ether described below, dissolved in 420 parts 7 of dioxane, werejintroduced'dropwise inthe-course of about lVz -Zhours, while sturing. The dioxane was then distilled oil? under reduced pressure. There was obtained an approximately colorless product of mediumvis'cosity,

which no longer contains epoxide groups, and had an,v

2 mols of caustic soda, and the product was washed and dried. JThe resulting product of medium viscosity contained about 4.7 Ep-Equ/kg, about 10.7 Y-Equ/kg and about 1.3 OH-Equ/kg;

' 'Example 2, V V The procedure was the same as that describedin Example 1, except that after the distillation of the dioxane parts of the unreacted linseed oil fatty alcohol were removed by distillation under apressnre of about 3 mm. Hg and at an external temperature of 240 to 285 C.

(oil bath). There were obtained 880partsof an approximately colorless reaction product of medium viscosity at about 20 C. and containing 2.34 OH-Equ/kg. 7

Example 3 -A mixture of 540parts ofoctadecyl alcohol (2 mols) A and about 0.21 part of boron trifiuoride dissolved '-in anisole was heated to about "70 C. A mixture of 416 parts (1.95 Ep-Equ) of'fthe. polyglycidyl ether described in the second paragraph of. Example 1 and 416 parts of dioxane wasadded -dropwise to the octadecyljalcohol in -,the course of about 2hours'whilev stirring. The die oxane was then distilled off under. reduced pressure on awater bath.; No epoxide groups-could be .detected in the resulting product..1'84 parts of the unreacted octadecyl alcohol were distilled elf-under reduced pressure I at an oilibathfte'mperature of at most 270- 'C. There -were obtained 772 parts of the wax-like, solid and pale brown product freed from excess of octadecyl alcohol and containing 12.4 .OH-Equ/kg, anda softening point of- '43 Cidetermined by the method 'of Kr'almer-Sarnow; Exampla4 f f V V The procedure wast he same as that described in Ex ample, 3, except that, instead of 540 parts of octadecyl alcohol, there; were 11S6d540 parts of lsoya' .bean vfatty alcohol, and instead; of 0.21 part of boron trifluqride O.325 part of boron trifluoride,-and that the removal "of the unreacted alcohol was :dispensed with; The product free from epoxide groups contained 2.9 oH-Equ /k g. and had agood compatibility with white spirit. V In admixture with, advantageouslyetherified,,formaldehyde condensation products of urea, aminotriazines or phenols, the aboveproduct is suitableifor producing lacquers baking at a, te nperature'of 180,'220 C. .De'pending 'on the quantity and nature of the ,componentsuse'd and on the baking time and temperature, there are ob tained slightly pale yellow to gold-yellow coatings of good elasticity and surface hardness, and also gloss and resistance to chemicals and water.

Example 5 A mixture of 576 parts (2 mols) of abietin alcohol and about 0.82 part of boron trifiuoride dissolved in anisole was heated on the water bath at 97 C. A solution of 820 parts (2 Ep-Equ) of the polyglycidyl ether described below in 820 parts of dioxane was added dropwise to the abietin alcohol in the course of about 2 hours while stirring well.

The dioxane was then distilled off under reduced pressure, and the unreacted 216 parts of abietin alcohol were removed from the reaction mixture under a pressure of about 2 mm. Hg and at an oil bath temperature of about 300 C. There were obtained 1120 parts of a product resembling colophony free from epoxide groups and insoluble in white spirit which had a softening point of 8081 C. according to Kr'almer-Sarnow and containing 2.75 OH-Equ/kg. By boiling the resulting resin with a mixture of linseed oil, wood oil and stand oil there can be obtained a lacquer base soluble in white spirit, which dries well after the addition of a drier and has good film-forming properties.

The polyglycidyl ether used in this example was prepared as follows:

228 parts of dihydroxydiphenyl-dimethyl methane (1 mol) were reacted with 148 parts of epichlorhydrin (1.6 mol) in the presence of an aqueous solution of caustic soda, and the product was washed and dried. The re-' sulting brittle resin contained about 2.4 Ep-Equ/kg.

Example 6 A mixture of 100 parts (0.635 Ep-Equ) of a polyglycidyl ether of glycol, prepared as described below, and 632 parts (2.3 mols) of linseed oil fatty alcohol was heated in an atmosphere of nitrogen for about 5 hours on an oil bath having a temperature of about 280300 C. While still warm the reaction product was filtered through a layer of filtration earth, and then the unreacted linseed oil fatty alcohol was distilled from the filtrate under a pressure of about 5 mm. Hg at an oil bath temperature of about 280 C. There were obtained about 300 parts of a brown, epoxide-free etherification product of medium viscosity containing 2.9 OH-Equ/kg. The product is soluble in white spirit and has good oven-drying properties after the addition of a drier.

The above etherification reaction can also be carried out by continually controlling the decrease in the content of epoxide groups and interrupting the etherification by cooling at the instant at which the product has the desired content of epoxide groups. Thus, for example, by interrupting the reaction after heating for 1% hours a product is obtained which contains 0.1 Ep-Equ/kg.

The polyglycidyl ether of glycol containing 6.35 Ep-Equ/kg. used in this example was prepared from glycol and epichlorhydrin as described on page 5 of British specification No. 518,057. In this manner there was obtained, not as might be supposed from the aforesaid specification the unitary diglycidyl ether of glycol, but a mixture of high molecular polyglycidyl ethers of glycol.

Example 7 720 parts of the etherification product obtained as described in Example 1, after the addition of 3 parts of aqueous hypophosphorous acid of about 60 percent strength, were heated in an atmosphere of carbon dioxide or nitrogen at an oil bath temperature of about 310 C. for about 5% hours under a pressure of 170-250 mm. Hg, while stirring. The viscosity increased due to the polymerization, so that a highly viscous and pale brown product was obtained which is suitable, for example, as a lacquer base. It contained about 2.7 OH-Equ/kg. A

6 solution of this product of about 40 percent strength in a mixture of 15 parts of white spirit and 1 part of toluene mixed with a suitable drier, after being poured on to a glass plate, left a lacquer film which dried at room temperature in about 3 /2 to 4 hours, which film was distinguished by its good resistance to alkali.

Example 8 In a manner similar to that described in Example 7, the etherification product obtained as described in Example 2 was polymerized with the application of heat. The polymerization product so obtained had practically the same properties as the product of Example 7.

ExampleQ 104 parts of linseed oil fatty alcohol, which had an iodine number of about 165, were mixed with 0.885 part of a solution 12 percent strength of boron tn'fluoride in anisole. Into this mixture there was slowly introduced dropwise, while stirring well, in the course of about 1 hour a solution of 106 parts of the polyglycidyl ether described in the second paragraph of Example 1 in 106 parts of dioxane. The mixture, which initially had a temperature of about 20 C., was then stirred for a further 3 hours during which it heated up to about 40 C. From the epoxide-free solution the dioxane was then distilled ofi on a water bath under reduced pressure in the course of about 2 hours. There were obtained about 216 parts of a pale yellow viscous etherification product having an iodine number of about and containing about 2.5 HO-Equ/kg.

A solution of about 50 percent strength of the resulting product in white spirit containing a suitable drier, when poured on to a glass plate, left a dust-dry coating r after standing at room temperature for 3 /2 hours.

Example 10 75 parts of the etherification product obtained as described in the first paragraph of Example 4 were heated, in order to react the hydroxyl groups present, with 25 parts of a melamine-formaldehyde condensation product containing about 5 methoxymethyl groups for about 5% hours with the introduction of carbon dioxide and at about -150 C. (internal temperature) under a pressure of about 700 mm. Hg. The resulting highly viscous product contained about 1.2 HO-Equ/kg.

The above product was dissolved in its own weight of white spirit, mixed with 0.5 percent of lead and 0.1 percent of cobalt in the form of their naphthenates as driers, and then poured for example on to glass and after being maintained for about 1% hours at 22 C. a dust-dry coating having good lacquer properties was obtained.

Example 11 41.8 parts of commercial linseed oil fatty alcohol glycerine diether, prepared in the manner described below, were heated with parts of a solution of 5.2 percent strength of boron trifiuoride in anisole at about 70 C., while stirring. To the solution there were added dropwise in the course of 25 minutes at a temperature of about 7075 C., while stirring, a solution of 21.5 parts of the polyglycidyl ether mentioned in the second paragraph of Example 1 in 64.5 parts of dioxane. The temperature was maintained for a further 55 minutes .at about 7075 C., whereupon epoxide groups could no longer be detected in the reaction product. By the addition of a 1 N-alcoholic solution of caustic soda (about 4 parts by volume), the boron trifiuoride was decomposed, and then the dioxane was distilled off on the water bath under reduced pressure. The resulting etherification product was a yellowish highly viscous mass soluble, for example, in toluene.

The commercial linseed oil fatty alcohol glycerine diether used in this example was prepared as follows:

35.2 parts (0.88 mol) of sodium hydroxide was dispresence; of butyl alcohol.

solved -v while stirring at'about 100110;C; in 43 2 parts (l,6 3--m,ols) of a mixture of linseedoil fatty alcohols 1 prepared-from linseed'oil by reduction with sodium in the 37 parts (0.4 mol) of epichlorhydrin wereadded dropwise in thejcourse of about one hour to the resulting solution at a temperature of about 100-105 C., while. stirring. The temperature. of the reaction mass was maintained at about 150 C. for a further 3 hours, then' the caustiqsodasolution lwas neutralized with aqueous concentrated hydrochloric acid, and the precipitated sodium' chloride was filtered off. The residue on the filter was washed with petroleum ether,-

and thersolvent and unreacted linseed oil fatty alcohol were distilled from the combined filtrates under reduced pressure. 7 After washing the resulting. product with methanol and distilling. ofi'the latter, 175 parts of com mercial linseed 'oil fatty. alcohol glycerine diether having anjOH'-Equ/kg'. of about 2.3 were obtainedp What is claimed is:

I 1. A composition of mattercomprising the reaction 7 product of (a) the etherification productof a polyglycidyl ether with-a higher monohydric alcohol containing a :carbon chain of more than 10 carbon atoms, said polyglycidyl ether being a polyglycidyl ether of a polyhy-I "drox'y compound whichcontains at least two hydroxyl groups and its free from other substituents capable'of reacting with epoxide groups, said etherification product being free from epoxy groups, and '(b) condensation products containingmethylol groups obtained from formaldehyde and a compound of the group consisting of o 9, Pa e 5- phenolgurea aminotriazme at Ileast. 2

NH -groups, the methylol groups of'thelcondensatiori Y products being at'least partially etherified with a lower" alcohol containing 1-4" carbon atoms.

5;. 22..Azbohipositidn' of matter comprising 'ltherea'ction V product of (a)'the etherification product of a polyglycidyl 1 Leth'er witli'fa higher monohydric alcohol containing a carbon chainjof more than.10 carbon atom's,-'said polyglycidyl lethenbeing' a polyglycidyl ether ofia polyhy-. 10v droxy'compound which contains at least two hydroxyl groups and is free from otheresubstituents capable of V reactingwith epoxide groups, saidetherification product .being. free from? epoxy. groups, and .(b) .a' melamine- V formaldehyde condensation product containing methylol. 15 groups of which at least a part is ethen'fied with methyl alcohol. I v V V A 4 ef n s Cited in the :file of this parent outrun stares PATENTS .OTHER REFERENCES 7 Epon Rsiiijs F Paint, Oil and Chemical Review, Nov. 

1. A COMPOSITION OF MATTER COMPRISING THE REACTION PRODUCT OF (A) THE ETHERIFICATION PRODUCT OF A POLYGLYCIDYL ETHER WITH A HIGHER MONOHYDRIC ALCOHOL CONTAINING A CARBON CHAIN OF MORE THAN 10 CARBON ATOMS, AND POLYGLYCIDYL ETHER BEING A POLYCLYCIDYL ETHER OF A POLYHYDROXY COMPOUND WHICH CONTAINS AT LEAST TWO HYDROXYL GROUPS AND ITS FREE FROM OTHER SUBSTITUENTS CAPABLE OF REACTING WITH EPOXIDE GROUPS, SAID ETHERIFICATION PRODUCT BEING FREE FROM EPOXY GROUPS, AND (B) CONDENSATION PRODUCTS CONTAINING METHYLOL GROUPS OBTAINED FROM FORMALDEHYDE AND A COMPOUND OF THE GROUP CONSISTING OF PHENOL, UREA AND AMINOTRIAZINE CONTAINING AT LEAST 2 NH2-GROUPS, AND METHYLOL GROUPS OF THE CONDENSATION PRODUCTS BEING AT LEAST PARTIALLY ETHERIFIED WITH A LOWER ALCOHOL CONTAINING 1-4 CARBON ATOMS. 